EP3045435B1 - Lithium silicate glass ceramic and glass with zro2 content - Google Patents
Lithium silicate glass ceramic and glass with zro2 content Download PDFInfo
- Publication number
- EP3045435B1 EP3045435B1 EP16159020.3A EP16159020A EP3045435B1 EP 3045435 B1 EP3045435 B1 EP 3045435B1 EP 16159020 A EP16159020 A EP 16159020A EP 3045435 B1 EP3045435 B1 EP 3045435B1
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- EP
- European Patent Office
- Prior art keywords
- glass
- glass ceramic
- ceramic
- ceramic according
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011521 glass Substances 0.000 title claims description 57
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 title claims description 44
- 229910052912 lithium silicate Inorganic materials 0.000 title claims description 43
- 239000006017 silicate glass-ceramic Substances 0.000 title claims description 11
- 239000002241 glass-ceramic Substances 0.000 claims description 78
- 239000013078 crystal Substances 0.000 claims description 45
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 22
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 21
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 21
- 239000011224 oxide ceramic Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000002667 nucleating agent Substances 0.000 claims description 8
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 4
- 239000005548 dental material Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 2
- 229910052681 coesite Inorganic materials 0.000 claims 2
- 229910052593 corundum Inorganic materials 0.000 claims 2
- 229910052906 cristobalite Inorganic materials 0.000 claims 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims 2
- 239000000377 silicon dioxide Substances 0.000 claims 2
- 229910052682 stishovite Inorganic materials 0.000 claims 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims 2
- 229910052905 tridymite Inorganic materials 0.000 claims 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 2
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims 1
- 229910000417 bismuth pentoxide Inorganic materials 0.000 claims 1
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 claims 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims 1
- 229910001953 rubidium(I) oxide Inorganic materials 0.000 claims 1
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 description 25
- 239000000919 ceramic Substances 0.000 description 24
- 238000002425 crystallisation Methods 0.000 description 12
- 230000008025 crystallization Effects 0.000 description 12
- 239000003103 lithium disilicate glass Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000003825 pressing Methods 0.000 description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000007731 hot pressing Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 229910018068 Li 2 O Inorganic materials 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000006065 metasilicate glass ceramic Substances 0.000 description 8
- 238000001483 high-temperature X-ray diffraction Methods 0.000 description 7
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000006136 disilicate glass ceramic Substances 0.000 description 5
- 238000003754 machining Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000156 glass melt Substances 0.000 description 4
- 238000007669 thermal treatment Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- 244000052616 bacterial pathogen Species 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910007746 Zr—O Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- -1 oxides Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
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- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
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Definitions
- the invention relates to lithium silicate glass-ceramic containing ZrO 2 and is particularly suitable for coating zirconium oxide ceramic.
- Zirconia ceramics are characterized by excellent biocompatibility and excellent mechanical properties, which is why they have been used in recent years increasingly as a material for implants and prostheses, but also as framework materials for dental restorations.
- ceramics based on partially stabilized zirconium oxide are used.
- Glass ceramics have been used in the past for coating or veneering oxide ceramics, such as zirconium oxide ceramics. These include feldspar-based ceramics or fluoroapatite glass ceramics.
- lithium disilicate glass ceramics which find application in particular in the dental field and thereby primarily for the production of dental crowns and small bridges due to their high translucency and very good mechanical properties.
- the EP 1 505 041 describes lithium silicate glass ceramics, which may additionally contain 0 to 2 wt .-% ZrO 2 . These are processed in particular in the form of lithium metasilicate glass ceramics by means of CAD / CAM processes to the desired dental restorations, wherein a subsequent heat treatment causes the conversion of the metasilicate phase in the high-strength disilicate phase.
- the glass-ceramics can also be used for over-pressing of ceramic restorations.
- the EP 1 688 398 describes similar lithium silicate glass-ceramics, which are substantially free of ZnO and may contain 0 to 4 wt .-% ZrO 2 , among other components. However, small amounts of 0 to 2 wt .-% ZrO 2 are preferred for achieving high strengths. These glass ceramics are also used in particular for the production of dental restorations after mechanical processing by means of CAD / CAM.
- lithium silicate glass ceramics known from the prior art have the disadvantage that they are not suitable for coating zirconium oxide ceramics, in particular by means of a press-on operation in the viscous state. Because after pressing through the viscous flow process, cracks and cracks develop in the glass ceramic. Thus, such a composite does not have the mechanical properties that are essential for use as a dental restorative material.
- Glass ceramics with lithium disilicate as the main crystal phase known to be suitable for veneering dental restorations of yttrium stabilized zirconia.
- these glass ceramics contain only amounts of up to 6.0 wt .-% of ZrO 2 and substantial amounts of Na 2 O.
- the existing ZrO 2 serves only as a classical nucleating agent together with optional other nucleating such as TiO 2 , to the formation bring about the desired lithium disilicate crystal phase.
- the EP 0 690 031 discloses glass-ceramics with 15-28 wt% ZrO 2 .
- the invention has for its object to provide a glass ceramic available, which can be coated in particular by pressing in the viscous state on a zirconia and thereby forms a substantially free of cracks and cracks coating.
- the glass-ceramic should be able to form a solid bond with the zirconia ceramic to be coated, and it should have optical and mechanical properties to be used in particular as a coating material for dental restorations but also as a material for dental restorations.
- the invention likewise provides the process for producing the glass ceramic according to claim 10, the use according to claims 11 and 12, the dental restoration according to claim 13 and the coated zirconium oxide ceramic according to claim 14.
- the lithium silicate glass-ceramic according to the invention is characterized in that it contains 8.0 to 16.0% by weight ZrO 2 and 0.5 to 3.5% by weight Al 2 O 3 and lithium metasilicate as the main crystal phase and in the form of a monolithic blank.
- the glass ceramic contains in particular 10.0 to 16.0 wt .-% ZrO 2 .
- a glass-ceramic containing 9.0 to 17.0 and in particular 11 to 15 wt .-% Li 2 O is preferred.
- the glass ceramic contains 0.5 to 12.0 and in particular 2.5 to 7.0 wt .-% nucleating agent.
- Preferred nucleating agents are selected from P 2 O 5 , TiO 2 , Nb 2 O 5 , metals, for example Pt, Pd, Au and Ag, or mixtures thereof.
- the glass ceramic particularly preferably contains P 2 O 5 as nucleating agent.
- P 2 O 5 as a nucleating agent causes the formation of desired lithium disilicate crystals and on the other hand largely avoids the formation of ZrO 2 -containing crystal phases, which could considerably impair the translucency. Also, the use of other unwanted secondary crystal phases apparently largely avoided by its use.
- the glass-ceramic of the invention preferably contains further alkali metal oxide in an amount of 1.0 to 7.0, preferably 2.0 to 7.0, and more preferably 2.0 to 5.0 wt .-%.
- the term "further alkali metal oxide” refers to alkali metal oxide with the exception of Li 2 O.
- the further alkali metal oxide is in particular K 2 O, Cs 2 O and / or Rb 2 O and is particularly preferably K 2 O. It is assumed that the use of K 2 O contributes to the strengthening of the glass network compared to the used in conventional glass-ceramics Na 2 O. It is preferred that the glass-ceramic contains less than 2.0, in particular less than 1.0, preferably less than 0.5 and particularly preferably substantially no Na 2 O.
- the glass-ceramic contains up to 5.0% by weight of alkaline earth metal oxide, wherein the alkaline earth metal oxide is, in particular, CaO, BaO, MgO, SrO or a mixture thereof.
- a glass ceramic which contains 0.5 to 10.0, in particular 2.5 to 7.0, and preferably 2.5 to 3.5,% by weight of oxide of trivalent elements is furthermore preferred, this oxide being in particular selected from Al 2 O 3 , Y 2 O 3 , La 2 O 3 , Bi 2 O 3 and mixtures thereof, and preferably Al 2 O 3 .
- a glass ceramic which contains at least one and preferably all the following components: component Wt .-% SiO 2 55.0 to 71.0 Li 2 O 9.0 to 17.0 K 2 O 1.0 to 7.0, especially 2.0 to 5.0 Al 2 O 3 0.5 to 3.5 P 2 O 5 0.5 to 12.0, especially 2.5 to 7.0 ZrO 2 8.0 to 16.0.
- the glass-ceramic according to the invention may additionally contain additional components, which are in particular selected from further oxides of tetravalent elements, further oxides of pentavalent elements, oxides of hexavalent elements, melt accelerators, colorants and fluorescers.
- further oxides of tetravalent elements refers to oxides of tetravalent elements except SiO 2 and ZrO 2 . Examples of further oxides of tetravalent elements are SnO 2 and GeO 2 .
- pentavalent elements refers to oxides of pentavalent elements except P 2 O 5 .
- An example of another oxide of pentavalent elements is Bi 2 O 5 .
- oxides of hexavalent elements are WO 3 and MoO 3 .
- melt accelerators are fluorides.
- colorants and fluorescers are oxides of d and f elements, e.g. the oxides of Ti, Sc, Mn, Fe, Ag, Ta, W, Ce, Pr, Nd, Tb, Er and Yb.
- main crystal phase refers to the crystal phase which has the highest volume fraction compared to other crystal phases.
- the glass-ceramic according to the invention has lithium metasilicate as main crystal phase.
- the glass ceramic contains more than 10% by volume, preferably more than 20% by volume and particularly preferably more than 30% by volume of lithium metasilicate crystals, based on the total glass ceramic.
- This glass ceramic can be converted by heat treatment into a glass ceramic having lithium disilicate as the main crystal phase.
- the glass ceramic contains more than 10% by volume, preferably more than 20% by volume and particularly preferably more than 30% by volume, of lithium disilicate crystals, based on the total glass ceramic.
- the lithium disilicate glass ceramic is distinguished by particularly good mechanical properties and can be produced by heat treatment of the lithium metasilicate glass ceramic according to the invention.
- the lithium disilicate glass ceramic despite its high content of ZrO 2 advantageous mechanical parameters, such as high fracture toughness values and in particular pressing in the viscous state can be applied to zirconia without causing it to tension in the Glass ceramic comes, which are noticeable by cracks or cracks. It is particularly surprising that these very good mechanical properties are achieved, although the structure of the glass-ceramic lithium disilicate crystals which are not crosslinked with each other in the rule. Such crosslinking, on the other hand, occurs in the known lithium disilicate glass-ceramics and is considered to be an essential reason for their high strengths.
- the ZrO 2 in the glass-ceramic of the invention does not serve as a nucleating agent for other crystal phases unlike in known products, but rather amplifies the glass network via Zr-O polyhedrons incorporated therein.
- These polyhedra may be [ZrO 6/2 ] 2- or [ZrO 8/2 ] 4- structural units that function as network formers or network transducers.
- lithium disilicate glass ceramic despite its high content of ZrO 2 has a high translucency and no amorphous-amorphous phase separation occurs in her and they can thus be used for aesthetically pleasing coating of particular dental restorations based on zirconia.
- the lithium disilicate crystals present in the lithium disilicate glass ceramic have in particular the form of platelets. It is believed that this special morphology enables the crack-free composite with zirconia ceramics. The critical stress build-up in the composite material during the thermal cooling phase seems to be less pronounced in the platelet-shaped crystal form than in lithium disilicate glass ceramics with elongated or needle-shaped crystals. In addition, with the platelet-shaped crystal morphology, a good fracture toughness, expressed by the K IC value, is achieved.
- the lithium disilicate glass ceramic has a fracture toughness, measured as K IC value, of at least 1.5 MPa ⁇ m 0.5 and in particular more than 1.8 MPa ⁇ m 0.5 . Further, it has a high biaxial breaking strength of preferably 200 to 500 MPa. Moreover, it shows a high chemical resistance, the was determined by mass loss after storage in acetic acid. The chemical resistance is in particular less than 60 ⁇ g / cm 2 . Finally, it has a linear thermal expansion coefficient of in particular less than 10.3 ⁇ 10 -6 K -1 m / m, measured in the range of 100 to 500 ° C, which is thus regularly lower than that of the zirconium oxide ceramic to be coated.
- the starting glass, the glass with nuclei and the lithium metasilicate glass-ceramic can be regarded as precursors for producing the high-strength lithium disilicate glass-ceramic.
- the invention also relates to a process for the preparation of a glass-ceramic which contains 8.0 to 16.0% by weight of ZrO 2 and 0.5 to 3.5% by weight of Al 2 O 3 and has lithium metasilicate as the main crystal phase, in which a starting glass with the components the glass-ceramic is subjected in the form of a solid glass blank at least one heat treatment in the range of 450 to 950 ° C.
- the starting glass therefore contains 8.0 to 16.0 wt .-% ZrO 2 and 0.5 to 3.5 wt .-% Al 2 O 3 .
- it preferably also contains suitable amounts of SiO 2 and Li 2 O, in order to allow the formation of a lithium silicate glass-ceramic.
- the starting glass may also contain other components, as indicated above for the lithium silicate glass ceramic according to the invention. In this case, those embodiments are preferred which are also indicated as preferred for the glass-ceramic.
- the starting glass is prepared by mixing a mixture of suitable starting materials, e.g. Carbonates, oxides, phosphates and fluorides, is melted at temperatures of in particular 1300 to 1600 ° C for 2 to 10 h.
- suitable starting materials e.g. Carbonates, oxides, phosphates and fluorides
- the glass melt obtained is poured into water to form a glass granulate, and the granules obtained are then remelted.
- the melt is then poured into molds to produce blanks of the starting glass, so-called solid glass blanks or monolithic blanks.
- the starting glass in the form of a solid glass blank is subjected to at least one heat treatment in the range from 450 to 950 ° C. It is preferred that initially at a temperature in the range of 500 to 600 ° C, a first Heat treatment is carried out to produce a glass with germs, which are suitable for the formation of lithium metasilicate crystals. This glass may then preferably be subjected to at least one further temperature treatment at a higher temperature, and in particular more than 570 ° C, to effect crystallization of lithium metasilicate.
- the at least one heat treatment carried out in the process according to the invention can also be carried out in the context of pressing the glass according to the invention or the glass ceramic according to the invention onto the selected zirconium oxide ceramic.
- dental restorations such as inlays, onlays, crowns, veneers, shells or abutments
- the invention therefore also relates to the use thereof for the production of dental restorations.
- the glass ceramic is deformed by pressing or machining to the desired dental restoration.
- the compression is usually carried out under elevated pressure and elevated temperature.
- the lithium metasilicate glass ceramic according to the invention can be used in a suitable manner in the form of blanks for the pressing.
- the machining is usually carried out within the framework of a CAD / CAM method, and in particular uses the lithium metasilicate glass ceramic according to the invention in the form of suitable blanks.
- the glass ceramic according to the invention is particularly suitable for coating zirconium oxide ceramics.
- the invention is therefore likewise directed to the use of the glass ceramic according to the invention for coating zirconium oxide ceramics.
- the coating of zirconium oxide ceramic can be carried out by a method in which the glass ceramic according to the invention is applied to the zirconium oxide ceramic and exposed to elevated temperature.
- pressing the glass-ceramic according to the invention in the form of monolithic blanks at an elevated temperature, for example, 700 to 1200 ° C, and using pressure, for example 2 to 10 bar, pressed.
- pressure for example 2 to 10 bar
- a suitable furnace is eg the Programat EP 5000 from Ivoclar Vivadent AG, Liechtenstein.
- the above-described glass ceramic with lithium disilicate is present as the main crystal phase, since it has particularly good properties. It is surprisingly found that the glass-ceramic has virtually no cracks and cracks after it has been coated on the zirconia ceramic, and a strong bond between glass-ceramic and ceramic is achieved.
- the zirconia ceramic for stabilizing the tetragonal phase at least one oxide of Ce, Y, Sr, Ca or Mg.
- the zirconia ceramic may also be in the form of a composite with other inorganic components.
- the zirconium oxide ceramic coated with the glass ceramic according to the invention represents a further subject of the invention.
- the invention therefore also relates to the use of the glass ceramic according to the invention as a dental material and in particular for the production of dental restorations or as a coating material for dental restorations, such as crowns and bridges.
- the coated zirconia ceramic is a strong composite of one hand, high-strength and high-strength zirconia and on the other hand tough glass ceramic, which is why this composite is capable of high load pick-up in the chewing cycle.
- the glass-ceramic according to the invention can advantageously also be used in the coating of long-span bridges with more than three members based on zirconium oxide ceramic.
- a total of 20 glasses and glass ceramics with the composition given in Tables I to IV were prepared by melting corresponding starting glasses and subsequent heat treatment for controlled nucleation and crystallization.
- the starting glasses were first melted in 100 to 200 g scale from conventional raw materials at 1400 to 1500 ° C and converted into glass frits by pouring into water. These glass frits were then melted for a second time at 1450 to 1550 ° C for 1 to 3 hours for homogenization. The resulting glass melts were poured into preheated molds to produce glass monoliths. These glass monoliths were converted by thermal treatment to glasses and glass ceramics.
- the applied thermal treatment for controlled nucleation and controlled crystallization is given in Table V for selected examples.
- the first heat treatment in the range of 500 to 560 ° C led to the formation of lithium silicate glasses with nuclei for lithium metasilicate or lithium disilicate crystals, the second heat treatment at 650 to 710 ° C to form lithium metasilicate glass ceramics and the third heat treatment in Range of 800 to 920 ° C to form lithium disilicate glass-ceramics.
- a second non-isothermal heat treatment was carried out with simultaneous analysis of the crystal phases formed at the particular temperature indicated by high-temperature X-ray diffraction (HT-XRD).
- HT-XRD high-temperature X-ray diffraction
- the crystal phases obtained after completion of all heat treatments are also listed in Table V. Surprisingly, glass ceramics with lithium disilicate as the main crystal phase were always obtained. Examples 4 and 5 were additionally repeated by performing only the first and second heat treatments. In this way, glass ceramics were produced with lithium metasilicate as the main crystal phase.
- a glass having the composition according to Example 4 was prepared by mixing corresponding raw materials in the form of oxides and carbonates in a Turbola mixer for 30 minutes and then melting them at 1450 ° C. for 120 minutes in a platinum crucible. The melt was poured into water to obtain finely divided glass granules. This glass granulate was again melted at 1530 ° C for 150 minutes to obtain a glass melt having a particularly high homogeneity. The temperature was lowered to 1500 ° C for 30 minutes and then cylindrical glass blanks 12.5 mm in diameter were poured into preheated, divisible steel molds or graphite molds. Thereafter, the obtained glass cylinders were relaxed at 550 ° C. A glass with nuclei for lithium metasilicate or lithium disilicate crystals was obtained.
- the FIG. 1 shows the result of differential thermal analysis (DSC) of a crushed glass cylinder.
- FIG. 2 shows by means of high-temperature X-ray diffraction (HT-XRD) of a glass cylinder the dependence of the formation of lithium metasilicate (Li2SiO3) and lithium disilicate (Li2Si2O5) from the temperature.
- HT-XRD high-temperature X-ray diffraction
- the glass cylinders were then subjected to a first crystallization at 680 to 700 ° C for 20 minutes. The heating rate was 15 ° C per minute. The glass cylinders were then subjected to a second crystallization at 850 to 880 ° C for 30 minutes.
- the crystal phase analysis after this treatment showed a glass ceramic with lithium disilicate as the main crystal phase and small amounts of lithium metasilicate and lithium phosphate as secondary phases.
- FIG. 3 shows a scanning electron micrograph (SEM) of a crystallized cylinder which has been polished and etched for 30 seconds with HF vapor.
- the crystallized cylinders were further processed into test specimens by hot pressing at a press temperature of 910 ° C. using an EP600 press oven, Ivoclar Vivadent AG.
- the properties of these test specimens were as follows: Colour: white translucent without fluorescence Solubility: 24 ⁇ g / cm 2 (according to ISO 6872 of 1 September 2008) biaxial: 420 MPa (according to ISO 6872 of 1 September 2008) Fracture Toughness: 2.0 MPam 0.5 (determined as K IC value according to the SEVNB method according to ISO 6872 of 1 September 2008) Thermal expansion coefficient: 9.9 * 10 -6 * 1 / K (in the range 100 to 500 ° C)
- the lithium disilicate glass ceramic according to Example 4 was pressed onto the zirconium oxide ceramic of type 3 Y-TZP, obtainable from Tosoh, by heating at 920 ° C. in a combined press and furnace Programat EP 5000 from Ivoclar Vivadent AG, Liechtenstein, on zirconium oxide ceramic. After completion of the coating process, a defect-free addition resulted.
- FIG. 4 shows a scanning electron micrograph (SEM) of this composite after etching with 40% HF vapor.
- the objects were embrittled with a sandblaster, which due to the high strength of the coated glass-ceramic no special care was required.
- the objects were separated from the press channels, dry-worked with a diamond grinder, and then placed under IPS INVEX Liquid (Ivoclar Vivadent AG) for 20 minutes Treated with ultrasound to dissolve remaining residues of investment, which were then blasted with Al 2 O 3 sand of grain size 100 microns at 1-2 bar pressure.
- Example 21 was repeated with the difference that it was assumed that a glass having the composition according to Example 15.
- the resulting crystallized cylinders were further processed by hot pressing at a temperature of 905 ° C to test specimens.
- the properties of these test specimens were as follows: Colour: tooth-colored translucent with tooth-like fluorescence Solubility: 30 ⁇ g / cm 2 (according to ISO 6872 of 1 September 2008) biaxial: 405 MPa (according to ISO 6872 of 1 September 2008) Thermal expansion coefficient: 9.9 * 10 -6 * 1 / K (in the range 100 to 500 ° C)
- Example 23 was repeated with the difference that the crystallized cylinders according to Example 24 were used. After up to four final glaze firings, crowns and bridges were obtained, which in turn showed no cracks, bubbles or lifts.
- Glasses having the composition according to Examples 2, 3 and 4 were first prepared by mixing corresponding raw materials in the form of oxides and carbonates in a Turbola mixer for 30 minutes and then melting them at 1450 ° C. for 120 minutes in a platinum crucible. The melts were poured into water to obtain finely divided glass granules. These glass granules were again melted at 1530 ° C for 150 minutes to obtain glass melts with particularly high homogeneity. The temperature was lowered to 1500 ° C for 30 minutes and then a) cuboid (12.5mm x 14mm x 40mm) and b) cylindrical glass blanks with a diameter of 12.5mm were poured into preheated divisible steel molds or graphite molds. Thereafter, the obtained glass cubes or glass cylinders were heat-treated in the range of 500-560 ° C, depending on the composition, to form nuclei for lithium metasilicate and / or lithium disilicate crystals and to relax the glass.
- the resulting ingots with seeds were further processed into restorations according to the following alternatives.
- the glass cubes with seeds (A) were first subjected to a first crystallization according to (B) (ii) to effect the crystallization of lithium metasilicate.
- mechanical dental restorations such as inlays, onlays, crowns, partial crowns, shells and Veeners, were then worked out by means of CAD / CAM methods, eg Sirona, Cerec 2® or Cerec 3®.
- these restorations were subjected to a second crystallization at 840 to 880 ° C for 5 minutes to 1 hour.
- the crystal phase analysis after this treatment showed a glass ceramic with lithium disilicate as the main crystal phase.
- the HT-XRD analysis used a heating rate of about 2 K / min.
Description
Die Erfindung betrifft Lithiumsilikat-Glaskeramik, die ZrO2 enthält und sich insbesondere zum Beschichten von Zirkonoxidkeramik eignet.The invention relates to lithium silicate glass-ceramic containing ZrO 2 and is particularly suitable for coating zirconium oxide ceramic.
Zirkonoxidkeramiken zeichnen sich durch ausgezeichnete Biokompatibilität und hervorragende mechanische Eigenschaften aus, weshalb sie in den vergangenen Jahren in zunehmenden Umfang als Werkstoff für Implantate und Prothesen, aber auch als Gerüstwerkstoffe für dentale Restaurationen eingesetzt worden sind. Dabei werden vornehmlich Keramiken auf Basis von teilstabilisiertem Zirkonoxid verwendet.Zirconia ceramics are characterized by excellent biocompatibility and excellent mechanical properties, which is why they have been used in recent years increasingly as a material for implants and prostheses, but also as framework materials for dental restorations. In this case, mainly ceramics based on partially stabilized zirconium oxide are used.
In vielen Fällen ist es wünschenswert, die Oberfläche der Zirkonoxidkeramik durch Beschichtung mit einem anderen Material zu verändern. Gerade bei der Herstellung von dentalen Restaurationen auf Basis von Zirkonoxidkeramik wird eine solche Beschichtung regelmäßig verwendet, um der Restauration die gewünschten optischen Eigenschaften zu verleihen.In many cases it is desirable to change the surface of the zirconia ceramic by coating it with another material. Especially in the manufacture of dental restorations based on zirconium oxide ceramic is such Coating regularly used to give the restoration the desired optical properties.
Zur Beschichtung oder Verblendung von Oxidkeramiken, wie Zirkonoxidkeramiken, sind in der Vergangenheit bereits Glaskeramiken eingesetzt worden. Dazu zählen auf Feldspat basierende Keramiken oder Fluoroapatit-Glaskeramiken.Glass ceramics have been used in the past for coating or veneering oxide ceramics, such as zirconium oxide ceramics. These include feldspar-based ceramics or fluoroapatite glass ceramics.
Weiter sind Lithiumdisilikat-Glaskeramiken bekannt, die aufgrund ihrer hohen Transluzenz und sehr guten mechanischen Eigenschaften besonders im Dentalbereich und dabei vornehmlich zur Herstellung von Dentalkronen und kleinen Brücken Anwendung finden.Furthermore, lithium disilicate glass ceramics are known, which find application in particular in the dental field and thereby primarily for the production of dental crowns and small bridges due to their high translucency and very good mechanical properties.
Die
Die
Diese aus dem Stand der Technik bekannten Lithiumsilikat-Glaskeramiken besitzen allerdings den Nachteil, dass sie nicht zum Beschichten von Zirkonoxidkeramik insbesondere mittels eines Aufpressvorgangs im viskosen Zustand geeignet sind. Denn nach dem Aufpressen durch den viskosen Fließvorgang entstehen Risse und Sprünge in der Glaskeramik. Somit hat ein derartiger Verbund nicht die mechanischen Eigenschaften, die gerade für den Einsatz als dentales Restaurationsmaterial unabdingbar sind.However, these lithium silicate glass ceramics known from the prior art have the disadvantage that they are not suitable for coating zirconium oxide ceramics, in particular by means of a press-on operation in the viscous state. Because after pressing through the viscous flow process, cracks and cracks develop in the glass ceramic. Thus, such a composite does not have the mechanical properties that are essential for use as a dental restorative material.
Weiter sind aus der
Ausgehend von den oben beschriebenen Nachteilen der bereits bekannten Glaskeramiken liegt der Erfindung die Aufgabe zugrunde, eine Glaskeramik zur Verfügung zu stellen, die insbesondere durch Aufpressen im viskosen Zustand auf eine Zirkonoxidkeramik geschichtet werden kann und dabei eine im wesentlichen von Rissen und Sprüngen freie Beschichtung bildet. Überdies soll die Glaskeramik in der Lage sein, einen festen Verbund mit der zu beschichtenden Zirkonoxidkeramik auszubilden, und sie soll über optische und mechanische Eigenschaften verfügen, um insbesondere als Beschichtungsmaterial für dentale Restaurationen aber auch als Werkstoff für dentale Restaurationen eingesetzt werden zu können.Based on the above-described disadvantages of the already known glass ceramics, the invention has for its object to provide a glass ceramic available, which can be coated in particular by pressing in the viscous state on a zirconia and thereby forms a substantially free of cracks and cracks coating. Moreover, the glass-ceramic should be able to form a solid bond with the zirconia ceramic to be coated, and it should have optical and mechanical properties to be used in particular as a coating material for dental restorations but also as a material for dental restorations.
Diese Aufgabe wird durch die Lithiumsilikat-Glaskeramik nach einem der Ansprüche 1 bis 9 gelöst. Gegenstand der Erfindung sind ebenfalls das Verfahren zur Herstellung der Glaskeramik nach Anspruch 10, die Verwendung nach den Ansprüchen 11 und 12, die dentale Restauration nach Anspruch 13 und die beschichtete Zirkonoxidkeramik nach Anspruch 14.This object is achieved by the lithium silicate glass-ceramic according to one of claims 1 to 9. The invention likewise provides the process for producing the glass ceramic according to claim 10, the use according to claims 11 and 12, the dental restoration according to claim 13 and the coated zirconium oxide ceramic according to claim 14.
Die erfindungsgemäße Lithiumsilikat-Glaskeramik zeichnet sich dadurch aus, dass sie 8,0 bis 16,0 Gew.-% ZrO2 und 0,5 bis 3,5 Gew.-% Al2O3 enthält
und Lithiummetasilikat als Hauptkristallphase aufweist und in Form eines monolithischen Rohlings vorliegt.The lithium silicate glass-ceramic according to the invention is characterized in that it contains 8.0 to 16.0% by weight ZrO 2 and 0.5 to 3.5% by weight Al 2 O 3
and lithium metasilicate as the main crystal phase and in the form of a monolithic blank.
In einer weiteren bevorzugten Ausführungsform enthält die Glaskeramik insbesondere 10,0 bis 16,0 Gew.-% ZrO2.In a further preferred embodiment, the glass ceramic contains in particular 10.0 to 16.0 wt .-% ZrO 2 .
Bevorzugt ist weiter eine Glaskeramik, die 55,0 bis 71,0, bevorzugt 60,0 bis 71,0 und insbesondere 60 bis 69 Gew.-% SiO2 enthält.Preference is further given to a glass ceramic containing 55.0 to 71.0, preferably 60.0 to 71.0 and in particular 60 to 69 wt .-% SiO 2 .
Außerdem ist eine Glaskeramik bevorzugt, die 9,0 bis 17,0 und insbesondere 11 bis 15 Gew.-% Li2O enthält.In addition, a glass-ceramic containing 9.0 to 17.0 and in particular 11 to 15 wt .-% Li 2 O is preferred.
Weiter hat es sich als besonders bevorzugt erwiesen, wenn die Glaskeramik 0,5 bis 12,0 und insbesondere 2,5 bis 7,0 Gew.-% Keimbildner enthält. Bevorzugte Keimbildner sind ausgewählt aus P2O5, TiO2, Nb2O5, Metallen, z.B. Pt, Pd, Au und Ag, oder Mischungen davon. Besonders bevorzugt enthält die Glaskeramik P2O5 als Keimbildner. Überraschenderweise bewirkt insbesondere P2O5 als Keimbildner die Ausbildung von gewünschten Lithiumdisilikat-Kristallen und vermeidet auf der anderen Seite weitgehend die Bildung von ZrO2-haltigen Kristallphasen, die die Transluzenz erheblich verschlechtern könnten. Auch wird durch seine Verwendung offenbar die Ausbildung von anderen unerwünschten Nebenkristallphasen weitgehend vermieden.Furthermore, it has proven to be particularly preferred if the glass ceramic contains 0.5 to 12.0 and in particular 2.5 to 7.0 wt .-% nucleating agent. Preferred nucleating agents are selected from P 2 O 5 , TiO 2 , Nb 2 O 5 , metals, for example Pt, Pd, Au and Ag, or mixtures thereof. The glass ceramic particularly preferably contains P 2 O 5 as nucleating agent. Surprisingly, in particular, P 2 O 5 as a nucleating agent causes the formation of desired lithium disilicate crystals and on the other hand largely avoids the formation of ZrO 2 -containing crystal phases, which could considerably impair the translucency. Also, the use of other unwanted secondary crystal phases apparently largely avoided by its use.
Die erfindungsgemäße Glaskeramik enthält bevorzugt weiteres Alkalimetalloxid in einer Menge von 1,0 bis 7,0, bevorzugt 2,0 bis 7,0 und besonders bevorzugt 2,0 bis 5,0 Gew.-%. Der Begriff "weiteres Alkalimetalloxid" bezeichnet Alkalimetalloxid mit Ausnahme von Li2O. Das weitere Alkalimetalloxid ist insbesondere K2O, Cs2O und/oder Rb2O und ist besonders bevorzugt K2O. Es wird angenommen, dass der Einsatz von K2O gegenüber dem in konventionelle Glaskeramiken eingesetzten Na2O zur Verstärkung des Glasnetzwerkes beiträgt. Es ist bevorzugt, dass die Glaskeramik weniger als 2,0, insbesondere weniger als 1,0, bevorzugt weniger als 0,5 und besonders bevorzugt im Wesentlichen kein Na2O enthält.The glass-ceramic of the invention preferably contains further alkali metal oxide in an amount of 1.0 to 7.0, preferably 2.0 to 7.0, and more preferably 2.0 to 5.0 wt .-%. The term "further alkali metal oxide" refers to alkali metal oxide with the exception of Li 2 O. The further alkali metal oxide is in particular K 2 O, Cs 2 O and / or Rb 2 O and is particularly preferably K 2 O. It is assumed that the use of K 2 O contributes to the strengthening of the glass network compared to the used in conventional glass-ceramics Na 2 O. It is preferred that the glass-ceramic contains less than 2.0, in particular less than 1.0, preferably less than 0.5 and particularly preferably substantially no Na 2 O.
Weiter ist es bevorzugt, dass die Glaskeramik bis zu 5,0 Gew.-% Erdalkalimetalloxid enthält, wobei das Erdalkalimetalloxid insbesondere CaO, BaO, MgO, SrO oder eine Mischung davon ist.Further, it is preferable that the glass-ceramic contains up to 5.0% by weight of alkaline earth metal oxide, wherein the alkaline earth metal oxide is, in particular, CaO, BaO, MgO, SrO or a mixture thereof.
Es ist weiter eine Glaskeramik bevorzugt, die 0,5 bis 10,0, insbesondere 2,5 bis 7,0 und bevorzugt 2,5 bis 3,5 Gew.-% Oxid dreiwertiger Elemente enthält, wobei dieses Oxid insbesondere ausgewählt ist aus Al2O3, Y2O3, La2O3, Bi2O3 und Mischungen davon, und bevorzugt Al2O3 ist.A glass ceramic which contains 0.5 to 10.0, in particular 2.5 to 7.0, and preferably 2.5 to 3.5,% by weight of oxide of trivalent elements is furthermore preferred, this oxide being in particular selected from Al 2 O 3 , Y 2 O 3 , La 2 O 3 , Bi 2 O 3 and mixtures thereof, and preferably Al 2 O 3 .
Besonders bevorzugt ist eine Glaskeramik, die mindestens eine und bevorzugt alle folgenden Komponenten enthält:
Die erfindungsgemäße Glaskeramik kann darüber hinaus noch Zusatzkomponenten enthalten, die insbesondere ausgewählt sind aus weiteren Oxiden vierwertiger Elemente, weiteren Oxiden fünfwertiger Elemente, Oxiden sechswertiger Elemente, Schmelzbeschleunigern, Färbemitteln und Fluoreszenzmitteln.The glass-ceramic according to the invention may additionally contain additional components, which are in particular selected from further oxides of tetravalent elements, further oxides of pentavalent elements, oxides of hexavalent elements, melt accelerators, colorants and fluorescers.
Der Begriff "weitere Oxide vierwertiger Elemente" bezeichnet Oxide vierwertiger Elemente mit Ausnahme von SiO2 und ZrO2. Beispiele für weitere Oxide vierwertiger Elemente sind SnO2 und GeO2.The term "further oxides of tetravalent elements" refers to oxides of tetravalent elements except SiO 2 and ZrO 2 . Examples of further oxides of tetravalent elements are SnO 2 and GeO 2 .
Der Begriff "weitere Oxide fünfwertiger Elemente" bezeichnet Oxide fünfwertiger Elemente mit Ausnahme von P2O5. Ein Beispiel für ein weiteres Oxid fünfwertiger Elemente ist Bi2O5.The term "further oxides of pentavalent elements" refers to oxides of pentavalent elements except P 2 O 5 . An example of another oxide of pentavalent elements is Bi 2 O 5 .
Beispiele für Oxide sechswertiger Elemente sind WO3 und MoO3.Examples of oxides of hexavalent elements are WO 3 and MoO 3 .
Bevorzugt ist eine Glaskeramik, die mindestens ein weiteres Oxid vierwertiger Elemente, ein weiteres Oxid fünfwertiger Elemente oder ein Oxid sechswertiger Elemente enthält.Preference is given to a glass ceramic which contains at least one further oxide of tetravalent elements, a further oxide of pentavalent elements or an oxide of hexavalent elements.
Beispiele für Schmelzbeschleuniger sind Fluoride.Examples of melt accelerators are fluorides.
Beispiel für Färbemittel und Fluoreszenzmittel sind Oxide von d- und f-Elementen, wie z.B. die Oxide von Ti, Sc, Mn, Fe, Ag, Ta, W, Ce, Pr, Nd, Tb, Er und Yb.Examples of colorants and fluorescers are oxides of d and f elements, e.g. the oxides of Ti, Sc, Mn, Fe, Ag, Ta, W, Ce, Pr, Nd, Tb, Er and Yb.
Der im Folgenden verwendete Begriff "Hauptkristallphase" bezeichnet die Kristallphase, die gegenüber anderen Kristallphasen den höchsten Volumenanteil hat.The term "main crystal phase" used hereinafter refers to the crystal phase which has the highest volume fraction compared to other crystal phases.
Die erfindungsgemäße Glaskeramik weist Lithiummetasilikat als Hauptkristallphase auf. Insbesondere enthält die Glaskeramik mehr als 10 Vol.-%, bevorzugt mehr als 20 Vol.-% und besonders bevorzugt mehr als 30 Vol.-% an Lithiummetasilikat-Kristallen, bezogen auf die gesamte Glaskeramik.The glass-ceramic according to the invention has lithium metasilicate as main crystal phase. In particular, the glass ceramic contains more than 10% by volume, preferably more than 20% by volume and particularly preferably more than 30% by volume of lithium metasilicate crystals, based on the total glass ceramic.
Diese Glaskeramik kann durch Wärmebehandlung in eine Glaskeramik umgewandelt werden, die Lithiumdisilikat als Hauptkristallphase aufweist. Insbesondere enthält die Glaskeramik mehr als 10 Vol.-%, bevorzugt mehr als 20 Vol.-% und besonders bevorzugt mehr als 30 Vol.-% an Lithiumdisilikat-Kristallen, bezogen auf die gesamte Glaskeramik.This glass ceramic can be converted by heat treatment into a glass ceramic having lithium disilicate as the main crystal phase. In particular, the glass ceramic contains more than 10% by volume, preferably more than 20% by volume and particularly preferably more than 30% by volume, of lithium disilicate crystals, based on the total glass ceramic.
Die Lithiumdisilikat-Glaskeramik zeichnet sich durch besonders gute mechanische Eigenschaften aus und sie kann durch Wärmebehandlung der erfindungsgemäßen Lithiummetasilikat-Glaskeramik erzeugt werden.The lithium disilicate glass ceramic is distinguished by particularly good mechanical properties and can be produced by heat treatment of the lithium metasilicate glass ceramic according to the invention.
Es hat sich überraschenderweise gezeigt, dass die Lithiumdisilikat-Glaskeramik trotz ihres hohen Gehalts an ZrO2 vorteilhafte mechanische Parameter, wie hohe Bruchzähigkeits-Werte hat und insbesondere Aufpressen im viskosen Zustand auf Zirkonoxidkeramik aufgebracht werden kann, ohne dass es dabei zu Verspannungen in der
Glaskeramik kommt, die sich durch Risse oder Sprünge bemerkbar machen. Es ist dabei besonders überraschend, dass diese sehr guten mechanischen Eigenschaften erzielt werden, obwohl das Gefüge der Glaskeramik Lithiumdisilikat-Kristalle aufweist, die in der Regel nicht miteinander vernetzt sind. Eine derartige Vernetzung tritt hingegen bei den bekannten Lithiumdisilikat-Glaskeramiken auf und sie wird als wesentlicher Grund für deren hohe Festigkeiten angesehen. Es wird derzeit angenommen, dass das ZrO2 in der erfindungsgemäßen Glaskeramik anders als in bekannten Produkten nicht als Keimbildner für andere Kristallphasen dient, sondern vielmehr das Glasnetzwerk über darin eingebaute Zr-O-Polyeder verstärkt. Diese Polyeder können [ZrO6/2]2-- oder [ZrO8/2]4- Struktureinheiten sein, die als Netzwerkbildner oder Netzwerkwandler fungieren.It has surprisingly been found that the lithium disilicate glass ceramic despite its high content of ZrO 2 advantageous mechanical parameters, such as high fracture toughness values and in particular pressing in the viscous state can be applied to zirconia without causing it to tension in the
Glass ceramic comes, which are noticeable by cracks or cracks. It is particularly surprising that these very good mechanical properties are achieved, although the structure of the glass-ceramic lithium disilicate crystals which are not crosslinked with each other in the rule. Such crosslinking, on the other hand, occurs in the known lithium disilicate glass-ceramics and is considered to be an essential reason for their high strengths. It is currently believed that the ZrO 2 in the glass-ceramic of the invention does not serve as a nucleating agent for other crystal phases unlike in known products, but rather amplifies the glass network via Zr-O polyhedrons incorporated therein. These polyhedra may be [ZrO 6/2 ] 2- or [ZrO 8/2 ] 4- structural units that function as network formers or network transducers.
Auch ist es überraschend, dass die Lithiumdisilikat-Glaskeramik trotz ihres hohen Gehalts an ZrO2 eine hohe Transluzenz besitzt und bei ihr keine Amorph-Amorph-Phasentrennung auftritt und sie damit zur ästhetisch ansprechenden Beschichtung von insbesondere dentalen Restaurationen auf Basis von Zirkonoxidkeramik eingesetzt werden kann.It is also surprising that the lithium disilicate glass ceramic despite its high content of ZrO 2 has a high translucency and no amorphous-amorphous phase separation occurs in her and they can thus be used for aesthetically pleasing coating of particular dental restorations based on zirconia.
Die in der Lithiumdisilikat-Glaskeramik vorhandenen Lithiumdisilikat-Kristalle haben insbesondere die Form von Plättchen. Es wird angenommen, dass diese spezielle Morphologie den rissfreien Werkstoffverbund mit Zirkonoxidkeramiken ermöglicht. Der kritische Spannungsaufbau im Werkstoffverbund während der thermischen Abkühlphase scheint bei der plättchenförmigen Kristallform weniger stark ausgeprägt zu sein als bei Lithiumdisilikat-Glaskeramiken mit länglichen oder nadelförmigen Kristallen. Zudem wird mit der plättchenförmigen Kristallmorphologie eine gute Bruchzähigkeit, ausgedrückt durch den KIC-Wert, erreicht.The lithium disilicate crystals present in the lithium disilicate glass ceramic have in particular the form of platelets. It is believed that this special morphology enables the crack-free composite with zirconia ceramics. The critical stress build-up in the composite material during the thermal cooling phase seems to be less pronounced in the platelet-shaped crystal form than in lithium disilicate glass ceramics with elongated or needle-shaped crystals. In addition, with the platelet-shaped crystal morphology, a good fracture toughness, expressed by the K IC value, is achieved.
Die Lithiumdisilikat-Glaskeramik hat insbesondere eine Bruchzähigkeit, gemessen als KIC Wert, von mindestens 1.5 MPa•m0.5 und insbesondere mehr als 1.8 MPa•m0.5. Weiter hat sie eine hohe biaxiale Bruchfestigkeit von bevorzugt 200 bis 500 MPa. Überdies zeigt sie eine hohe chemische Beständigkeit, die
durch Masseverlust nach Lagerung in Essigsäure ermittelt wurde. Die chemische Beständigkeit beträgt insbesondere weniger als 60 µg/cm2. Schließlich hat sie einen linearen thermischen Ausdehnungskoeffizienten von insbesondere weniger als 10,3 x 10-6 K-1 m/m, gemessen im Bereich von 100 bis 500°C, der damit regelmäßig geringer ist als der der zu beschichtenden Zirkonoxidkeramik.In particular, the lithium disilicate glass ceramic has a fracture toughness, measured as K IC value, of at least 1.5 MPa · m 0.5 and in particular more than 1.8 MPa · m 0.5 . Further, it has a high biaxial breaking strength of preferably 200 to 500 MPa. Moreover, it shows a high chemical resistance, the
was determined by mass loss after storage in acetic acid. The chemical resistance is in particular less than 60 μg / cm 2 . Finally, it has a linear thermal expansion coefficient of in particular less than 10.3 × 10 -6 K -1 m / m, measured in the range of 100 to 500 ° C, which is thus regularly lower than that of the zirconium oxide ceramic to be coated.
Durch Wärmebehandlung eines Ausgangsglases, das die Komponenten der erfindungsgemäßen Glaskeramik enthält, kann ein Lithiumsilikatglas mit Keimen erzeugt werden, die zur Ausbildung von Lithiummetasilikatkristallen geeignet sind. Durch eine weitere Wärmebehandlung kann dann die erfindungsgemäße Lithiummetasilikat-Glaskeramik gebildet werden, die ihrerseits durch weitere Wärmebehandlung in die oben beschriebene Lithiumdisilikat-Glaskeramik umgewandelt werden kann. Mithin können das Ausgangsglas, das Glas mit Keimen und die Lithiummetasilikat-Glaskeramik als Vorstufen zur Erzeugung der hochfesten Lithiumdisilikat-Glaskeramik angesehen werden.By heat-treating a starting glass containing the components of the glass ceramic according to the invention, it is possible to produce a lithium silicate glass having nuclei which are suitable for the formation of lithium metasilicate crystals. By a further heat treatment, the inventive lithium metasilicate glass ceramic can then be formed, which in turn can be converted by further heat treatment in the lithium disilicate glass ceramic described above. Thus, the starting glass, the glass with nuclei and the lithium metasilicate glass-ceramic can be regarded as precursors for producing the high-strength lithium disilicate glass-ceramic.
Die Erfindung betrifft ebenfalls ein Verfahren zur Herstellung einer Glaskeramik, die 8,0 bis 16,0 Gew.-% ZrO2 und 0,5 bis 3,5 Gew.-% Al2O3 enthält und Lithiummetasilikat als Hauptkristallphase aufweist, bei dem ein Ausgangsglas mit den Komponenten
der Glaskeramik in Form eines Massivglasrohlings mindestens einer Wärmebehandlung im Bereich von 450 bis 950°C unterzogen wird.The invention also relates to a process for the preparation of a glass-ceramic which contains 8.0 to 16.0% by weight of ZrO 2 and 0.5 to 3.5% by weight of Al 2 O 3 and has lithium metasilicate as the main crystal phase, in which a starting glass with the components
the glass-ceramic is subjected in the form of a solid glass blank at least one heat treatment in the range of 450 to 950 ° C.
Das Ausgangsglas enthält daher 8,0 bis 16,0 Gew.-% ZrO2 und 0,5 bis 3,5 Gew.-% Al2O3. Darüber hinaus enthält es bevorzugt auch geeignete Mengen an SiO2 und Li2O, um die Ausbildung einer Lithiumsilikat-Glaskeramik zu ermöglichen. Weiter kann das Ausgangsglas auch noch andere Komponenten enthalten, wie sie oben für die erfindungsgemäße Lithiumsilikat-Glaskeramik angegeben sind. Dabei sind solche Ausführungsformen bevorzugt, die auch für die Glaskeramik als bevorzugt angegeben sind.The starting glass therefore contains 8.0 to 16.0 wt .-% ZrO 2 and 0.5 to 3.5 wt .-% Al 2 O 3 . In addition, it preferably also contains suitable amounts of SiO 2 and Li 2 O, in order to allow the formation of a lithium silicate glass-ceramic. Furthermore, the starting glass may also contain other components, as indicated above for the lithium silicate glass ceramic according to the invention. In this case, those embodiments are preferred which are also indicated as preferred for the glass-ceramic.
Zur Herstellung des Ausgangsglases wird insbesondere so vorgegangen, dass eine Mischung von geeigneten Ausgangsmaterialien, wie z.B. Carbonaten, Oxiden, Phosphaten und Fluoriden, bei Temperaturen von insbesondere 1300 bis 1600°C für 2 bis 10 h erschmolzen wird. Zur Erzielung einer besonders hohen Homogenität wird die erhaltene Glasschmelze in Wasser gegossen, um ein Glasgranulat zu bilden, und das erhaltene Granulat wird dann erneut aufgeschmolzen. Die Schmelze wird dann in Formen gegossen, um Rohlinge des Ausgangsglases, sogenannte Massivglasrohlinge oder monolithische Rohlinge, zu erzeugen.In particular, the starting glass is prepared by mixing a mixture of suitable starting materials, e.g. Carbonates, oxides, phosphates and fluorides, is melted at temperatures of in particular 1300 to 1600 ° C for 2 to 10 h. To obtain a particularly high homogeneity, the glass melt obtained is poured into water to form a glass granulate, and the granules obtained are then remelted. The melt is then poured into molds to produce blanks of the starting glass, so-called solid glass blanks or monolithic blanks.
Anschließend wird das Ausgangsglas in Form eines Massivglasrohlings mindestens einer Wärmebehandlung im Bereich von 450 bis 950°C unterzogen. Es ist bevorzugt, dass zunächst bei einer Temperatur im Bereich von 500 bis 600°C eine erste Wärmebehandlung durchgeführt wird, um ein Glas mit Keimen herzustellen, welche zur Bildung von Lithiummetasilikatkristallen geeignet sind. Dieses Glas kann dann bevorzugt mindestens einer weiteren Temperaturbehandlung bei einer höheren Temperatur und insbesondere mehr als 570°C unterworfen werden, um Kristallisation von Lithiummetasilikat zu bewirken.Subsequently, the starting glass in the form of a solid glass blank is subjected to at least one heat treatment in the range from 450 to 950 ° C. It is preferred that initially at a temperature in the range of 500 to 600 ° C, a first Heat treatment is carried out to produce a glass with germs, which are suitable for the formation of lithium metasilicate crystals. This glass may then preferably be subjected to at least one further temperature treatment at a higher temperature, and in particular more than 570 ° C, to effect crystallization of lithium metasilicate.
Die im erfindungsgemäßen Verfahren durchgeführte mindestens eine Wärmebehandlung kann auch im Rahmen des Aufpressens des erfindungsgemäßen Glases oder der erfindungsgemäßen Glaskeramik auf die ausgewählte Zirkonoxidkeramik erfolgen.The at least one heat treatment carried out in the process according to the invention can also be carried out in the context of pressing the glass according to the invention or the glass ceramic according to the invention onto the selected zirconium oxide ceramic.
Aus den erfindungsgemäßen Glaskeramiken können dentale Restaurationen, wie Inlays, Onlays, Kronen, Veneers, Schalen oder Abutments, hergestellt werden. Die Erfindung betrifft daher auch deren Verwendung zur Herstellung dentaler Restaurationen. Dabei ist es bevorzugt, dass die Glaskeramik durch Verpressen oder maschinelle Bearbeitung zur gewünschten dentalen Restauration verformt wird. Das Verpressen erfolgt üblicherweise unter erhöhtem Druck und erhöhter Temperatur. Es können für das Verpressen vor allem die erfindungsgemäße Lithiummetasilikat-Glaskeramik in geeigneter Weise in Form von Rohlingen eingesetzt werden. Die maschinelle Bearbeitung wird üblicherweise im Rahmen eines CAD/CAM-Verfahrens durchgeführt, und sie nutzt insbesondere die erfindungsgemäße Lithiummetasilikat-Glaskeramik in Form von geeigneten Rohlingen. Nach der Herstellung der gewünscht geformten dentalen Restauration durch Verpressen oder maschinelle Bearbeitung kann diese insbesondere noch wärmebehandelt werden, um die Lithiummetasilikat-Glaskeramik in Lithiumdisilikat-Glaskeramik umzuwandeln.From the glass ceramics according to the invention, dental restorations, such as inlays, onlays, crowns, veneers, shells or abutments, can be produced. The invention therefore also relates to the use thereof for the production of dental restorations. It is preferred that the glass ceramic is deformed by pressing or machining to the desired dental restoration. The compression is usually carried out under elevated pressure and elevated temperature. Above all, the lithium metasilicate glass ceramic according to the invention can be used in a suitable manner in the form of blanks for the pressing. The machining is usually carried out within the framework of a CAD / CAM method, and in particular uses the lithium metasilicate glass ceramic according to the invention in the form of suitable blanks. After the production of the desired shaped dental restoration by pressing or machining, it can in particular still be heat treated in order to convert the lithium metasilicate glass ceramic into lithium disilicate glass ceramic.
Die erfindungsgemäße Glaskeramik eignet sich allerdings insbesondere zur Beschichtung von Zirkonoxidkeramiken. Die Erfindung ist daher ebenfalls auf die Verwendung der erfindungsgemäßen Glaskeramik zur Beschichtung von Zirkonoxidkeramiken gerichtet.The glass ceramic according to the invention, however, is particularly suitable for coating zirconium oxide ceramics. The invention is therefore likewise directed to the use of the glass ceramic according to the invention for coating zirconium oxide ceramics.
Die Beschichtung von Zirkonoxidkeramik kann durch ein Verfahren erfolgen, bei dem die erfindungsgemäße Glaskeramik auf die Zirkonoxidkeramik aufgebracht und erhöhter Temperatur ausgesetzt wird.The coating of zirconium oxide ceramic can be carried out by a method in which the glass ceramic according to the invention is applied to the zirconium oxide ceramic and exposed to elevated temperature.
Dies kann insbesondere durch Aufpressen erfolgen. Beim Aufpressen wird die erfindungsgemäße Glaskeramik in Form von monolithischen Rohlingen, bei einer erhöhten Temperatur, von z.B. 700 bis 1200°C, und unter Anwendung von Druck, z.B. 2 bis 10 bar, aufgepresst. Hierzu können insbesondere die in der
Es ist bevorzugt, dass nach Abschluss des Beschichtungsvorganges die oben beschriebene Glaskeramik mit Lithiumdisilikat als Hauptkristallphase vorliegt, da sie über besonders gute Eigenschaften verfügt. Es zeigt sich überraschenderweise, dass die Glaskeramik praktisch keine Sprünge und Risse aufweist, nachdem sie auf die Zirkonoxidkeramik geschichtet worden ist, und es wird ein fester Verbund zwischen Glaskeramik und Keramik erzielt.It is preferred that after completion of the coating process, the above-described glass ceramic with lithium disilicate is present as the main crystal phase, since it has particularly good properties. It is surprisingly found that the glass-ceramic has virtually no cracks and cracks after it has been coated on the zirconia ceramic, and a strong bond between glass-ceramic and ceramic is achieved.
Es ist bevorzugt, dass die Zirkonoxidkeramik zur Stabilisierung der tetragonalen Phase mindestens ein Oxid des Ce, Y, Sr, Ca oder Mg enthält. Die Zirkonoxidkeramik kann auch in Form eines Komposits mit anderen anorganischen Komponenten vorliegen.It is preferred that the zirconia ceramic for stabilizing the tetragonal phase at least one oxide of Ce, Y, Sr, Ca or Mg. The zirconia ceramic may also be in the form of a composite with other inorganic components.
Die mit der erfindungsgemäßen Glaskeramik beschichtete Zirkonoxidkeramik stellt einen weiteren Gegenstand der Erfindung dar.The zirconium oxide ceramic coated with the glass ceramic according to the invention represents a further subject of the invention.
Aufgrund der vorstehend geschilderten Eigenschaften der erfindungsgemäßen Glaskeramik eignet sich diese insbesondere auch zum Einsatz in der Zahnheilkunde. Gegenstand der Erfindung ist daher auch die Verwendung der erfindungsgemäßen Glaskeramik als Dentalmaterial und insbesondere zur Herstellung dentaler Restaurationen oder als Beschichtungsmaterial für dentale Restaurationen, wie Kronen und Brücken.Due to the above-described properties of the glass ceramic according to the invention, this is particularly suitable for use in dentistry. The invention therefore also relates to the use of the glass ceramic according to the invention as a dental material and in particular for the production of dental restorations or as a coating material for dental restorations, such as crowns and bridges.
Es ist überraschend, dass im Verbund zwischen der oben beschriebenen Lithiumdisilikat-Glaskeramik und Zirkonoxidkeramik keine Risse in der Glaskeramik auftreten. Es wird vermutet, dass insbesondere die spezielle plättchenförmige Morphologie der Lithiumdisilikatkristalle hierfür von Bedeutung ist. Der kritische Spannungsaufbau im Werkstoffverbund während der thermischen Abkühlphase scheint bei der plättchenförmigen Kristallform weniger stark ausgeprägt zu sein als bei Lithiumdisilikat-Glaskeramiken mit länglichen oder nadelförmigen Kristallen. Zudem wird insbesondere mit der plättchenartigen Kristallmorphologie eine gute Bruchzähigkeit von bis zu 2,1 MPa·m0,5 erreicht, obwohl im Gefüge im wesentlichen keine direkte Vernetzung der Lithiumdisilikat-Kristalle erkennbar ist. Damit ist die beschichtete Zirkonoxidkeramik ein starker Verbund aus einerseits hochfester und hochzäher Zirkonoxidkeramik und andererseits zäher Glaskeramik, weshalb dieser Verbund zu hohen Lastaufnahmen im Kauzyklus in der Lage ist. Damit kann die erfindungsgemäße Glaskeramik vorteilhaft auch gerade bei der Beschichtung von langspannigen Brücken mit mehr als drei Gliedern auf Basis von Zirkonoxidkeramik verwendet werden.It is surprising that no cracks in the glass ceramic occur in the composite between the lithium disilicate glass ceramic described above and zirconium oxide ceramic. It is believed that the particular platelet-shaped morphology of lithium disilicate crystals is of particular importance for this purpose. The critical stress build-up in the composite material during the thermal cooling phase seems to be less pronounced in the platelet-shaped crystal form than in lithium disilicate glass ceramics with elongated or needle-shaped crystals. In addition, a good fracture toughness of up to 2.1 MPa · m 0.5 is achieved, in particular with the platelet-like crystal morphology, although essentially no direct crosslinking of the lithium disilicate crystals is discernible in the microstructure. Thus, the coated zirconia ceramic is a strong composite of one hand, high-strength and high-strength zirconia and on the other hand tough glass ceramic, which is why this composite is capable of high load pick-up in the chewing cycle. Thus, the glass-ceramic according to the invention can advantageously also be used in the coating of long-span bridges with more than three members based on zirconium oxide ceramic.
Die Erfindung wird im Folgenden anhand von Beispielen näher erläutert.The invention will be explained in more detail below with reference to examples.
Es wurden insgesamt 20 Gläser und Glaskeramiken mit der aus den Tabellen I bis IV angegebenen Zusammensetzung über Erschmelzung entsprechender Ausgangsgläser und anschließende Wärmebehandlung zur gesteuerten Keimbildung und Kristallisation hergestellt.A total of 20 glasses and glass ceramics with the composition given in Tables I to IV were prepared by melting corresponding starting glasses and subsequent heat treatment for controlled nucleation and crystallization.
Dazu wurden zunächst die Ausgangsgläser im 100 bis 200 g Massstab aus üblichen Rohstoffen bei 1400 bis 1500°C erschmolzen und durch Eingießen in Wasser in Glasfritten umgewandelt. Diese Glasfritten wurden zur Homogenisierung anschließend ein zweites Mal bei 1450 bis 1550 °C für 1 bis 3 h geschmolzen. Die erhaltenen Glasschmelzen wurden in vorgewärmte Formen gegossen, um Glasmonolithe zu erzeugen. Diese Glasmonolithe wurden durch thermische Behandlung zu Gläsern und Glaskeramiken umgewandelt.For this purpose, the starting glasses were first melted in 100 to 200 g scale from conventional raw materials at 1400 to 1500 ° C and converted into glass frits by pouring into water. These glass frits were then melted for a second time at 1450 to 1550 ° C for 1 to 3 hours for homogenization. The resulting glass melts were poured into preheated molds to produce glass monoliths. These glass monoliths were converted by thermal treatment to glasses and glass ceramics.
Die angewandte thermische Behandlung zur gesteuerten Keimbildung und gesteuerten Kristallisation ist in der Tabelle V für ausgewählte Beispiele angegeben. Dabei führte in der Regel die erste Wärmebehandlung im Bereich von 500 bis 560°C zur Bildung von Lithiumsilikat-Gläsern mit Keimen für Lithiummetasilikat- oder Lithiumdisilikatkristalle, die zweite Wärmebehandlung bei 650 bis 710°C zur Bildung von Lithiummetasilikat-Glaskeramiken und die dritte Wärmebehandlung im Bereich von 800 bis 920°C zur Bildung von Lithiumdisilikat-Glaskeramiken.The applied thermal treatment for controlled nucleation and controlled crystallization is given in Table V for selected examples. As a rule, the first heat treatment in the range of 500 to 560 ° C led to the formation of lithium silicate glasses with nuclei for lithium metasilicate or lithium disilicate crystals, the second heat treatment at 650 to 710 ° C to form lithium metasilicate glass ceramics and the third heat treatment in Range of 800 to 920 ° C to form lithium disilicate glass-ceramics.
Bei einigen Beispielen wurde nach einer ersten Wärmebehandlung eine zweite nicht-isotherme Wärmebehandlung mit gleichzeitiger Analyse der gebildeten Kristallphasen bei der jeweils angegebenen Temperatur durch Hochtemperatur-Röntgenbeugung (HT-XRD) durchgeführt.In some examples, after a first heat treatment, a second non-isothermal heat treatment was carried out with simultaneous analysis of the crystal phases formed at the particular temperature indicated by high-temperature X-ray diffraction (HT-XRD).
Die nach Abschluß aller Wärmebehandlungen erhaltenen Kristallphasen sind ebenfalls in Tabelle V aufgeführt. Es wurden überraschenderweise stets Glaskeramiken mit Lithiumdisilikat als Hauptkristallphase erhalten. Die Beispiele 4 und 5 wurden zusätzlich wiederholt, indem lediglich die erste und zweite Wärmebehandlung durchgeführt wurden. Auf diese Weise wurden Glaskeramiken mit Lithiummetasilikat als Hauptkristallphase erzeugt.The crystal phases obtained after completion of all heat treatments are also listed in Table V. Surprisingly, glass ceramics with lithium disilicate as the main crystal phase were always obtained. Examples 4 and 5 were additionally repeated by performing only the first and second heat treatments. In this way, glass ceramics were produced with lithium metasilicate as the main crystal phase.
Es wurde ein Glas mit der Zusammensetzung gemäß Beispiel 4 hergestellt, indem entsprechende Rohstoffe in Form von Oxiden und Carbonaten 30 min in einem Turbola-Mischer gemischt und anschliessend bei 1450°C für 120 min in einem Platintiegel erschmolzen wurden. Die Schmelze wurde in Wasser gegossen, um ein feinteiliges Glasgranulat zu erhalten. Dieses Glasgranulat wurde erneut bei 1530°C für 150 min geschmolzen, um eine Glasschmelze mit besonders hoher Homogenität zu erhalten. Die Temperatur wurde für 30 min auf 1500°C abgesenkt und anschließend wurden zylindrische Glasrohlinge mit einem Durchmesser von 12.5 mm in vorgeheizte, teilbare Stahlformen oder Graphitformen gegossen. Danach wurden die erhaltenen Glaszylinder bei 550°C entspannt. Es wurde ein Glas mit Keimen für Lithiummetasilikat- oder Lithiumdisilikat-Kristalle erhalten.A glass having the composition according to Example 4 was prepared by mixing corresponding raw materials in the form of oxides and carbonates in a Turbola mixer for 30 minutes and then melting them at 1450 ° C. for 120 minutes in a platinum crucible. The melt was poured into water to obtain finely divided glass granules. This glass granulate was again melted at 1530 ° C for 150 minutes to obtain a glass melt having a particularly high homogeneity. The temperature was lowered to 1500 ° C for 30 minutes and then cylindrical glass blanks 12.5 mm in diameter were poured into preheated, divisible steel molds or graphite molds. Thereafter, the obtained glass cylinders were relaxed at 550 ° C. A glass with nuclei for lithium metasilicate or lithium disilicate crystals was obtained.
Die
Die
Die Glaszylinder wurden dann einer ersten Kristallisation bei 680 bis 700°C für 20 min unterworfen. Dabei betrug die Aufheizgeschwindigkeit 15°C pro Minute. Die Glaszylinder wurden anschließend einer zweiten Kristallisation bei 850 bis 880°C für 30 min unterworfen. Die Kristallphasenanalyse zeigte nach dieser Behandlung eine Glaskeramik mit Lithiumdisilikat als Hauptkristallphase sowie geringen Anteilen Lithiummetasilikat und Lithiumphosphat als Nebenphasen an.The glass cylinders were then subjected to a first crystallization at 680 to 700 ° C for 20 minutes. The heating rate was 15 ° C per minute. The glass cylinders were then subjected to a second crystallization at 850 to 880 ° C for 30 minutes. The crystal phase analysis after this treatment showed a glass ceramic with lithium disilicate as the main crystal phase and small amounts of lithium metasilicate and lithium phosphate as secondary phases.
Die
Die kristallisierten Zylinder wurden außerdem durch Heißpressen bei einer Presstemperatur von 910°C unter Verwendung eines Pressofens EP600, Ivoclar Vivadent AG, zu Prüfkörpern weiterverarbeitet. Die Eigenschaften dieser Prüfkörper waren wie folgt:
Durch Heisspressen wurde die Lithiumdisilikat-Glaskeramik gemäß Beispiel 4 bei 920°C in einem kombinierten Press- und Brennofen Programat EP 5000 der Firma Ivoclar Vivadent AG, Liechtenstein, auf Zirkonoxidkeramik vom Typ 3 Y-TZP, erhältlich von der Firma Tosoh, aufgepresst. Nach Abschluss des Beschichtungsvorganges ergab sich eine defektfreie Fügung.The lithium disilicate glass ceramic according to Example 4 was pressed onto the zirconium oxide ceramic of type 3 Y-TZP, obtainable from Tosoh, by heating at 920 ° C. in a combined press and furnace Programat EP 5000 from Ivoclar Vivadent AG, Liechtenstein, on zirconium oxide ceramic. After completion of the coating process, a defect-free addition resulted.
Einzelzahnkäppchen und viergliedrige Brückengerüste aus dicht gesintertem Zirkonoxid (e.max ZirCAD, Ivoclar Vivadent AG) wurden mit einem ausbrennbaren Kunststoff (PMMA) zu anatomisch geformten Restaurationen ergänzt. Sowohl die Brückengerüste als auch die Kunststoffteile wurden mittels CAD/CAM-Verfahren gefertigt, wodurch eine reproduzierbare Geometrie und Schichtdicke erzielt werden konnte. Die Restaurationen wurden in dentaler Einbettmasse (IPS PressVest Speed, Ivoclar Vivadent AG) eingebettet, der Kunststoff wurde ausgebrannt und die kristallisierten Zylinder gemäß Beispiel 21 wurden bei einer Temperatur von 910 °C direkt auf die Gerüste aufgepresst. Es wurde keine Zwischenschicht (Liner) auf das Zirkonoxid aufgebracht.Single-tooth copings and four-unit bridge frameworks made of densely sintered zirconium oxide (e.max ZirCAD, Ivoclar Vivadent AG) were supplemented with a burn-out plastic (PMMA) to form anatomically shaped restorations. Both the bridge frameworks and the plastic parts were manufactured using CAD / CAM processes, which allowed a reproducible geometry and layer thickness to be achieved. The restorations were embedded in dental investment material (IPS PressVest Speed, Ivoclar Vivadent AG), the plastic was burned out and the crystallized cylinders according to Example 21 were pressed directly onto the frameworks at a temperature of 910 ° C. No intermediate layer (liner) was applied to the zirconia.
Nach dem vollständigen Abkühlen wurden die Objekte mit einem Sandstrahlgerät ausgebettet, wobei aufgrund der hohen Festigkeit der aufgeschichteten Glaskeramik keine besondere Vorsicht erforderlich war. Die Objekte wurden von den Presskanälen abgetrennt, mit einem Diamantschleifer trocken überarbeitet, und dann 20 min mit IPS INVEX Liquid (Ivoclar Vivadent AG) unter Ultraschall behandelt, um noch verbliebene Reste an Einbettmasse zu lösen, welche dann mit Al2O3-Sand der Korngrösse 100 µm bei 1-2 bar Druck abgestrahlt wurden.After complete cooling, the objects were embrittled with a sandblaster, which due to the high strength of the coated glass-ceramic no special care was required. The objects were separated from the press channels, dry-worked with a diamond grinder, and then placed under IPS INVEX Liquid (Ivoclar Vivadent AG) for 20 minutes Treated with ultrasound to dissolve remaining residues of investment, which were then blasted with Al 2 O 3 sand of grain size 100 microns at 1-2 bar pressure.
Die Oberfläche wurden mit Heissdampf gereinigt und mit IPS e.max Ceram Glaze (Ivoclar Vivadent AG) bei 770°C zweimal glasiert, wodurch ein schöner Glanz erzeugt wurde. Bei den Glasurbränden wurde keine spezielle Abkühlung (Entspannungskühlung) angewandt. Die so hergestellten Restaurationen, d.h. Kronen und Brücken, waren ästhetisch ansprechend und fehlerfrei. Sie zeigten keine Risse, Blasen oder Abhebungen. Nach Aufsägen war im Querschnitt ein hervorragender Verbund zwischen der aufgeschichteten Lithiumdisilikat-Glaskeramik und dem Zirkonoxid mittels REM zu erkennen.The surface was cleaned with hot steam and twice glazed with IPS e.max Ceram Glaze (Ivoclar Vivadent AG) at 770 ° C, whereby a beautiful gloss was produced. In the glaze firings no special cooling (flash cooling) was used. The resulting restorations, i. Crowns and bridges were aesthetically pleasing and faultless. They showed no cracks, bubbles or lifts. After sawing, an excellent bond between the layered lithium disilicate glass-ceramic and the zirconium oxide could be seen in cross-section by means of SEM.
Jeweils 8 Kronen und 8 Brücken wurden in einer Kaumaschine (Willitec) mit 300.000 Zyklen bei Wasserlagerung unter Thermocycling von 5 auf 55 °C belastet. Die Prüfkraft betrug dabei während je 100.000 Zyklen 30, 60 bzw. 90 N. Die Belastung wurde mit einer Frequenz von 0.8 Hz aufgebracht. Hierbei zeigten sich keinerlei Abplatzungen (Chippings) in der Verblendstruktur.Each 8 crowns and 8 bridges were loaded in a compacting machine (Willitec) with 300,000 cycles with water storage under thermocycling from 5 to 55 ° C. The test force was during each 100,000 cycles 30, 60 and 90 N. The load was applied at a frequency of 0.8 Hz. This showed no chipping in the veneering structure.
Es wurde das Beispiel 21 mit dem Unterschied wiederholt, dass von einem Glas mit der Zusammensetzung gemäß Beispiel 15 ausgegangen wurde. Die erhaltenen kristallisierten Zylinder wurden durch Heisspressen bei einer Temperatur von 905°C zu Prüfkörpern weiterverarbeitet. Die Eigenschaften dieser Prüfkörper waren wie folgt:
Es wurde das Beispiel 23 mit dem Unterschied wiederholt, dass die kristallisierten Zylinder gemäß Beispiel 24 eingesetzt wurden. Nach bis zu vier abschließenden Glasurbränden wurden Kronen und Brücken erhalten, die wiederum keine Risse, Blasen oder Abhebungen zeigten.Example 23 was repeated with the difference that the crystallized cylinders according to Example 24 were used. After up to four final glaze firings, crowns and bridges were obtained, which in turn showed no cracks, bubbles or lifts.
Es wurden zunächst Gläser mit der Zusammensetzung gemäß Beispielen 2, 3 und 4 hergestellt, indem entsprechende Rohstoffe in Form von Oxiden und Carbonaten 30 min in einem Turbola-Mischer gemischt und anschließend bei 1450°C für 120 min in einem Platintiegel erschmolzen wurden. Die Schmelzen wurden in Wasser gegossen, um feinteilige Glasgranulate zu erhalten. Diese Glasgranulate wurden erneut bei 1530°C für 150 min geschmolzen, um Glasschmelzen mit besonders hoher Homogenität zu erhalten. Die Temperatur wurde für 30 min auf 1500°C abgesenkt und anschließend wurden a) quaderförmige (12.5mm x 14mm x 40mm) und b) zylindrische Glasrohlinge mit einem Durchmesser von 12.5mm in vorgeheizte, teilbare Stahlformen oder Graphitformen gegossen. Danach wurden die erhaltenen Glasquader oder Glaszylinder im Bereich von 500-560°C je nach Zusammensetzung wärmebehandelt, um Keime für Lithiummetasilikat- und/oder Lithiumdisilikat-Kristalle auszubilden und das Glas zu entspannen.Glasses having the composition according to Examples 2, 3 and 4 were first prepared by mixing corresponding raw materials in the form of oxides and carbonates in a Turbola mixer for 30 minutes and then melting them at 1450 ° C. for 120 minutes in a platinum crucible. The melts were poured into water to obtain finely divided glass granules. These glass granules were again melted at 1530 ° C for 150 minutes to obtain glass melts with particularly high homogeneity. The temperature was lowered to 1500 ° C for 30 minutes and then a) cuboid (12.5mm x 14mm x 40mm) and b) cylindrical glass blanks with a diameter of 12.5mm were poured into preheated divisible steel molds or graphite molds. Thereafter, the obtained glass cubes or glass cylinders were heat-treated in the range of 500-560 ° C, depending on the composition, to form nuclei for lithium metasilicate and / or lithium disilicate crystals and to relax the glass.
Die erhaltenen Rohlinge mit Keimen wurden gemäß der folgenden Alternativen zu Restaurationen weiterverarbeitet.The resulting ingots with seeds were further processed into restorations according to the following alternatives.
- i) Die Glaszylinder mit Keimen (A) wurden durch Heißpressen bei einer Presstemperatur von 900-950°C unter Verwendung eines Pressofens EP600, Ivoclar Vivadent AG, zu dentalen Restauration, wie Inlays, Onlays, Veneers, Teilkronen, Kronen und Schalen, verarbeitet. Als Hauptkristallphase konnte in den Restaurationen Lithiumdisilikat nachgewiesen werden.i) The glass cylinders with germs (A) were processed by hot pressing at a pressing temperature of 900-950 ° C using an EP600, Ivoclar Vivadent AG, to dental restorations, such as inlays, onlays, veneers, partial crowns, crowns and shells. As main crystal phase lithium disilicate could be detected in the restorations.
- ii) Die Glaszylinder mit Keimen (A) wurden einer ersten Kristallisation bei 650 bis 750°C für 20 min unterworfen. Dabei betrug die Aufheizgeschwindigkeit 15°C pro Minute. Nach dieser ersten Kristallisation konnte als Hauptkristallphase Lithiummetasilikat nachgewiesen werden. Durch Heißpressen der Lithiummetasilikat-Glaszylinder bei einer Presstemperatur von 900-950°C unter Verwendung eines Pressofens EP600, Ivoclar Vivadent AG, konnten dentale Restaurationen, wie Inlays, Onlays, Veneers, Teilkronen, Kronen und Schalen, hergestellt werden. Dabei wurde durch das Heißpressen Lithiummetasilikat in Lithiumdisilikat umgewandelt.ii) The glass cylinders with seeds (A) were subjected to a first crystallization at 650 to 750 ° C for 20 minutes. The heating rate was 15 ° C per minute. After this first crystallization, lithium metasilicate could be detected as the main crystal phase. By hot pressing the lithium metasilicate glass cylinder at a pressing temperature of 900-950 ° C using an EP600 press furnace, Ivoclar Vivadent AG, dental restorations, such as inlays, onlays, veneers, partial crowns, crowns and shells, could be produced. It was converted by the hot pressing lithium metasilicate in lithium disilicate.
- iii) Die Glaszylinder mit Keimen (A) wurden nach einer ersten Kristallisation gemäß ii) zusätzlich einer weiteren thermischen Behandlung bei 840 bis 880°C für 5 bis 30 min. unterworfen. Die Kristallphasenanalyse zeigte nach dieser Behandlung eine Glaskeramik mit Lithiumdisilikat als Hauptkristallphase. Die nach der zweiten Kristallisation erhaltenen kristallisierten Zylinder wurden anschließend durch Heißpressen bei einer Presstemperatur von 900-950°C unter Verwendung eines Pressofens EP600, Ivoclar Vivadent AG, zu dentalen Restaurationen, wie Inlays, Onlays, Veneers, Kronen, Teilkronen und Schalen, weiterverarbeitet.iii) The glass cylinders with seeds (A) were after a first crystallization according to ii) additionally a further thermal treatment at 840 to 880 ° C for 5 to 30 min. subjected. The crystal phase analysis after this treatment showed a glass ceramic with lithium disilicate as the main crystal phase. The crystallized cylinders obtained after the second crystallization were then hot pressed at a press temperature of 900-950 ° C using an EP600 press furnace, Ivoclar Vivadent AG, to dental restorations, such as inlays, onlays, veneers, crowns, partial crowns and shells, further processed.
Die Glasquader mit Keimen (A) wurden zunächst einer ersten Kristallisation gemäß (B)(ii) unterzogen, um die Kristallisation von Lithiummetasilikat zu bewirken. Aus den erhaltenen Lithiummetasilikat-Glasquadern wurden dann mittels CAD/CAM-Verfahren, z.B. Sirona, Cerec 2® oder Cerec 3®, maschinell dentale Restaurationen, wie Inlays, Onlays, Kronen, Teilkronen, Schalen und Veeners, herausgearbeitet. Anschließend wurden diese Restaurationen einer zweiten Kristallisation bei 840 bis 880°C für 5 min bis 1 h unterworfen. Die Kristallphasenanalyse zeigte nach dieser Behandlung eine Glaskeramik mit Lithiumdisilikat als Hauptkristallphase.
Bei der HT-XRD Analyse wurde eine Aufheizgeschwindigkeit von ca. 2 K/min verwendet.The HT-XRD analysis used a heating rate of about 2 K / min.
Claims (14)
- Lithium silicate glass ceramic, which comprises 8.0 to 16.0 wt.-% ZrO2 and 0.5 to 3.5 wt.-% Al2O3 and comprises lithium metasilicate as main crystalline phase and is present in the form of a monolithic blank.
- Glass ceramic according to claim 1, which comprises more than 10 vol.-%, preferably more than 20 vol.-% and particularly preferably more than 30 vol.-% of lithium metasilicate crystals.
- Glass ceramic according to claim 1 or 2, which comprises 55.0 to 71.0 and in particular 55.0 to 69.0 wt.-% SiO2.
- Glass ceramic according to any one of claims 1 to 3, which comprises 0.5 to 12.0 and in particular 2.5 to 7.0 wt.-% nucleating agent, wherein the nucleating agent is selected in particular from P2O5, TiO2, Nb2O5 and/or metals and preferably is P2O5.
- Glass ceramic according to any one of claims 1 to 4, which, apart from Li2O, comprises further alkali metal oxide in an amount of 1.0 to 7.0, preferably 2.0 to 7.0 and particularly preferably 2.0 to 5.0 wt.-%, wherein the further alkali metal oxide is in particular K2O, Cs2O and/or Rb2O and preferably is K2O.
- Glass ceramic according to any one of claims 1 to 5, which comprises up to 5.0 wt.-% alkaline earth metal oxide, wherein the alkaline earth metal oxide is preferably CaO, BaO, MgO and/or SrO.
- Glass ceramic according to any one of claims 1 to 6, which comprises 0.5 to 10.0, in particular 2.5 to 7.0 and preferably 2.5 to 3.5 wt.-% oxide of trivalent elements.
- Glass ceramic according to any one of claims 1 to 7, which comprises at least one further oxide of tetravalent elements, in particular SnO2 or GeO2, one further oxide of pentavalent elements, in particular Bi2O5, or one oxide of hexavalent elements, in particular WO3 or MoO3.
- Glass ceramic according to any one of claims 1 to 8, which comprises at least one and preferably all of the following components:
Component wt.-% SiO2 55.0 to 69.0 K2O 1.0 to 5.0 P2O5 0.5 to 12.0, in particular 2.5 to 7.0. - Process for preparing a lithium silicate glass ceramic, which comprises 8.0 to 16.0 wt.-% ZrO2 and 0.5 to 3.5 wt.-% Al2O3 and comprises lithium metasilicate as main crystalline phase, in which a starting glass with the components of the glass ceramic in the form of a solid glass blank is subjected to at least one heat treatment in the range of from 450 to 950°C.
- Use of the glass ceramic according to any one of claims 1 to 9 as a dental material and in particular for coating dental restorations and for preparing dental restorations.
- Use according to claim 11 for preparing dental inlays, onlays, veneers, partial crowns, crowns, facets or abutments.
- Dental restoration, which is coated with the glass ceramic according to any one of claims 1 to 9.
- Zirconium oxide ceramic, which is coated with the glass ceramic according to any one of claims 1 to 9.
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| EP16159020.3A EP3045435B1 (en) | 2010-04-16 | 2011-04-18 | Lithium silicate glass ceramic and glass with zro2 content |
| EP18202123.8A EP3453686B1 (en) | 2010-04-16 | 2011-04-18 | Use of a lithium silicate glass ceramic with zro2 content |
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| EP10160222 | 2010-04-16 | ||
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| EP11162840.0A EP2377831B1 (en) | 2010-04-16 | 2011-04-18 | Lithium silicate glass ceramic and glass with ZrO2 content |
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| EP18202123.8A Division EP3453686B1 (en) | 2010-04-16 | 2011-04-18 | Use of a lithium silicate glass ceramic with zro2 content |
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| EP18202123.8A Active EP3453686B1 (en) | 2010-04-16 | 2011-04-18 | Use of a lithium silicate glass ceramic with zro2 content |
| EP13179987.6A Active EP2664594B2 (en) | 2010-04-16 | 2011-04-18 | Lithium silicate glass ceramic and glass with ZrO2 content |
| EP13179984.3A Active EP2662342B1 (en) | 2010-04-16 | 2011-04-18 | Lithium silicate glass ceramic and glass with ZrO2 content |
| EP13179985.0A Active EP2662343B2 (en) | 2010-04-16 | 2011-04-18 | Lithium silicate glass ceramic and glass with ZrO2 content |
| EP20209410.8A Pending EP3848337A1 (en) | 2010-04-16 | 2011-04-18 | Lithium silicate glass ceramic and glass with zro2 content |
| EP11162840.0A Active EP2377831B1 (en) | 2010-04-16 | 2011-04-18 | Lithium silicate glass ceramic and glass with ZrO2 content |
| EP16159020.3A Active EP3045435B1 (en) | 2010-04-16 | 2011-04-18 | Lithium silicate glass ceramic and glass with zro2 content |
| EP11173131.1A Active EP2407439B1 (en) | 2010-04-16 | 2011-07-07 | Method for producing dental restorations |
| EP15162943.3A Active EP2913314B1 (en) | 2010-04-16 | 2011-07-07 | Method for producing dental restorations |
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| EP13179987.6A Active EP2664594B2 (en) | 2010-04-16 | 2011-04-18 | Lithium silicate glass ceramic and glass with ZrO2 content |
| EP13179984.3A Active EP2662342B1 (en) | 2010-04-16 | 2011-04-18 | Lithium silicate glass ceramic and glass with ZrO2 content |
| EP13179985.0A Active EP2662343B2 (en) | 2010-04-16 | 2011-04-18 | Lithium silicate glass ceramic and glass with ZrO2 content |
| EP20209410.8A Pending EP3848337A1 (en) | 2010-04-16 | 2011-04-18 | Lithium silicate glass ceramic and glass with zro2 content |
| EP11162840.0A Active EP2377831B1 (en) | 2010-04-16 | 2011-04-18 | Lithium silicate glass ceramic and glass with ZrO2 content |
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